Esd protection composite structure, esd protection device, and manufacturing method thereof

ABSTRACT

An ESD protection composite structure includes a link layer, a progressive layer, and a composite layer. The link layer is used for disposing the ESD protection composite structure on a substrate, wherein a material of the link layer includes a metal material. The progressive layer is disposed on the link layer, wherein the material of the progressive layer includes a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate in a thickness direction of the progressive layer. The composite layer is disposed on the progressive layer, wherein the composite layer includes a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer may make a sheet resistance value of the composite layer 1×10 7  Ω/sq to 1×10 8  Ω/sq.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the priority benefit of Taiwan application serial no. 107118025, filed on May 25, 2018. The entirety of the above-mentioned patent application is hereby incorporated by reference herein and made a part of this specification.

TECHNICAL FIELD

The disclosure relates to an ESD protection device and a manufacturing method thereof, and more particularly, to an ESD protection composite structure, an ESD protection device formed by the ESD protection composite structure, and a manufacturing method thereof.

BACKGROUND

In the current semiconductor industry, many related specifications and related materials of ESD protection have been developed. For instance, a conventional process and shipping process both have corresponding steps and materials, and even the humidity environment inside the factory is strictly regulated. However, in recent years, as electronic components have become smaller and more centralized, the circuit of the conductor equipment is more sophisticated, and spacing between wires is smaller, and therefore antistatic properties need to be improved.

In particular, in a high-temperature process, a carrier tray carrying a semiconductor device needs to tolerate a high-temperature environment (temperature resistance in prolonged use >300). To meet the demand of tolerating a high-temperature environment above, the carrier tray in a high-temperature process is still based on a metal material, but since the equivalent resistance of the metal material is low, once electrostatic discharge damage occurs, the discharge current thereof is large and the discharge duration is very short, such that significant damage to the device occurs. Therefore, an ESD protection material needs to be formed on the metal carrier tray to avoid the issue of damage to the semiconductor device on the carrier tray by the generation of electrostatic discharge.

The ESD protection material used here also needs to meet the demand for high-temperature resistance, but the ESD protection material meeting the demand of high-temperature resistance has issues such as the material itself is expensive, the process is complex such that production costs are high, and the mechanical properties of the resulting ESD protection material are still insufficient.

SUMMARY

The disclosure provides an ESD protection composite structure. The ESD protection composite structure includes a link layer, a progressive layer, and a composite layer. The link layer is used for disposing the ESD protection composite structure on a substrate, wherein a material of the link layer includes a metal material. The progressive layer is disposed on the link layer, wherein a material of the progressive layer includes a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate in a thickness direction of the progressive layer. The composite layer is disposed on the progressive layer, wherein the composite layer includes a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer may make a sheet resistance value of the composite layer 1×10⁷ Ω/sq to 1×10⁸ Ω/sq.

Moreover, the disclosure provides an ESD protection device. The ESD protection device includes a substrate and the ESD protection composite structure mentioned above, and the ESD protection composite structure is disposed on a substrate via a link layer.

Moreover, the disclosure provides a manufacturing method of an ESD protection device. The manufacturing method of the ESD protection device includes the following steps. A surface treatment is performed on the substrate. A link layer is formed on the substrate after the surface treatment, wherein a material of the link layer includes a metal material. A progressive layer is formed on the link layer, wherein a material of the progressive layer includes a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate in a thickness direction of the progressive layer. A composite layer is formed on the progressive layer, wherein the composite layer includes a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer may make a sheet resistance value of the composite layer 1×10⁷ Ω/sq to 1×10⁸ Ω/sq.

Several exemplary embodiments accompanied with figures are described in detail below to further describe the disclosure in details.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are included to provide further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments and, together with the description, serve to explain the principles of the disclosure.

FIG. 1A to FIG. 1D are schematics of the manufacturing process of a ESD protection device of an embodiment of the disclosure.

FIG. 2 shows a heating curve of a rapid thermal annealing (RTA) temperature test of the disclosure and a heating curve of an industrial reflow process.

FIG. 3 is a figure of current density versus film thickness of a corrosion resistance test of the disclosure.

DETAILED DESCRIPTION OF DISCLOSED EMBODIMENTS

FIG. 1A to FIG. 1D are schematics of the manufacturing process of an ESD protection device 10 of an embodiment of the disclosure.

Referring to FIG. 1A, a substrate 100 is provided, and a surface treatment 200 is performed on the substrate 100 to form a surface treatment layer 102 on a surface of the substrate 100. The substrate 100 is, for instance, a carrier tray for carrying a semiconductor device in a semiconductor process. The material of the substrate 100 is, for instance, a metal material, ceramic material, resin material, or a composite material of these materials. The metal material may be, for instance, stainless steel or aluminum, the ceramic material may be, for instance, TiO₂, Al₂O₃, CuO, NiO, Cr₂O₃, Ta₂O₅, or V₂O₅, and the resin material may be, for instance, polycarbonate, epoxy resin, polyvinyl chloride, polypropylene, or polyethylene terephthalate.

In some exemplary embodiments, the surface treatment 200 includes, for instance, disposing the substrate 100 in an arc ion plating apparatus, and performing surface treatment on the substrate 100 using oxygen/argon as a plasma to form the surface treatment layer 102 on the surface of the substrate 100. In some embodiments, the material of the substrate 100 is, for instance, aluminum or stainless steel, the ratio of oxygen/argon is, for instance, 0.5:1 to 1:0.5, the process bias is, for instance, 500 V to 900 V, and in some exemplary embodiments, the ratio of oxygen/argon is, for instance, 0.65:1 to 0.85:1, and the process bias is, for instance, 600 V to 800 V.

Next, referring to FIG. 1B, a link layer 110 is formed on the surface treatment layer 102 of the substrate 100, wherein the material of the link layer 110 includes a metal material. The metal material may be, for instance, a metal suitable for forming metal oxide (i.e., the so-called ceramic material) such as Ti, Al, Cu, Ni, Cr, Ta, or V.

In some exemplary embodiments, the forming of the link layer 110 includes, for instance, using the arc ion plating apparatus of the exemplary embodiment of FIG. 1A and the substrate 100 after the surface treatment and providing a metal target as the metal source to deposit a metal ion produced by the metal source on the surface treatment layer 102 of the substrate 100 to form the link layer 110 on the surface treatment layer 102 of the substrate 100. In some embodiments, the metal material in the link layer 100 may be, for instance, a Ti target, Al target, Cu target, Ni target, Cr target, Ta target, or V target. In some embodiments, the metal target is, for instance, a Ti target, the process current density is, for instance, 0.494 A/cm² to 0.988 A/cm², the process bias is, for instance, 100 V to 400 V, the thickness of the resulting link layer 110 is, for instance, 5 nm to 200 nm, and the link layer 110 is mainly formed by Ti.

Next, referring to FIG. 1C, a progressive layer 120 is formed on the link layer 110, wherein the material of the progressive layer 120 includes a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate 100 in a thickness direction of the progressive layer 120. The non-stoichiometric metal oxide material may be, for instance, TiOx, AlOx, CuOx, NiOx, CrOx, TaOx, or VOx, wherein 0<x<stoichiometry of metal oxide (in the case of TiOx, x is less than 2), and the value of x is gradually increased away from the substrate 100 in the thickness direction of the progressive layer 120.

In some exemplary embodiments, the forming of the progressive layer 120 includes, for instance, using the arc ion plating apparatus of the exemplary embodiment of FIG. 1B, the substrate 100 having the link layer 110 and the metal target, and providing oxygen as a reaction gas at the same time the metal ion is provided by the metal target to deposit the resulting non-stoichiometric metal oxide material on the link layer 110 so as to form the progressive layer 120 on the link layer 110, wherein the supply of oxygen is gradually increased with process time. In some embodiments, the metal target is, for instance, the same Ti target and has a process current density of, for instance, 0.494 A/cm² to 0.988 A/cm², a process bias of, for instance, 50 V to 300 V, and a supply of oxygen of, for instance, 60 sccm to 100 sccm, and the increasing trend is 5% to 10% every 10 minutes, the thickness of the resulting progressive layer 120 is, for instance, 50 nm to 500 nm, and the progressive layer 120 is mainly formed by TiOx (wherein 0<x<1.5).

Next, referring to FIG. 1D, a composite layer 130 is formed on the progressive layer 120, wherein the material of the composite layer 130 includes a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer 130 may make a sheet resistance value of the composite layer 130 1×10⁷ Ω/sq to 1×10⁸ Ω/sq. The stoichiometric metal oxide material may be, for instance, TiO₂, Al₂O₃, CuO, NiO, Cr₂O₃, Ta₂O₅, or V₂O₅. The non-stoichiometric metal oxide material may be, for instance, TiOx, AlOx, CuOx, NiOx, CrOx, TaOx, or VOx, wherein 0<x<stoichiometry of metal oxide. Moreover, the ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material that may make the sheet resistance value of the composite layer 130 1×10⁷ Ω/sq to 1×10⁸ Ω/sq is, for instance, 0.005:1 to 0.01:1.

The reason that the material of the composite layer 130 includes a stoichiometric metal oxide material and a non-stoichiometric metal oxide material is that the sheet resistance value of the stoichiometric metal oxide material is too high (about 1×10¹² Ω/sq in the case of TiO₂) such that the issue of being unsuitable for ESD protection application exists, and therefore in the disclosure, by mixing a non-stoichiometric metal oxide material of a specific ratio in the stoichiometric metal oxide material, the sheet resistance value of the composite layer 130 may be 1×10⁷ f′/sq to 1×10⁸ Ω/sq suitable for ESD protection application.

In some exemplary embodiments, the forming of the composite layer 130 includes, for instance, using the arc ion plating apparatus of the exemplary embodiment of FIG. 1C, the substrate 100 having the link layer 110 and the progressive layer 120, and the metal target, and providing oxygen as a reaction gas at the same time the metal ion is provided by the metal target to deposit the resulting stoichiometric metal oxide material and non-stoichiometric metal oxide material on the progressive layer 120 so as to form the composite layer 130 on the progressive layer 120, wherein the supply of oxygen is configured such that the ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the resulting composite layer 130 may make the sheet resistance value of the composite layer 130 1×10⁷ Ω/sq to 1×10⁸ Ω/sq. In some embodiments, the metal target is, for instance, the same Ti target and has a process current density of, for instance, 0.494 A/cm² to 0.988 A/cm², a process bias of, for instance, 50 V to 300 V, and a supply of oxygen of, for instance, 80 sccm to 150 sccm, the increasing trend is 8% to 15% every 10 minutes, the thickness of the resulting composite layer 130 is, for instance, 50 nm to 3000 nm, and the composite layer 130 is mainly formed by TiO₂ and TiOx, the ratio of TiOx and TiO₂ in the composite layer 130 is, for instance, 0.005:1 to 0.01:1, and the sheet resistance value of the composite layer 130 is, for instance, 1×10⁷ Ω/sq to 1×10⁸ Ω/sq.

Via the manufacturing method recited in FIG. 1A to FIG. 1D above, the ESD protection device 10 having the ESD protection composite structure 140 of the disclosure may be manufactured. Moreover, in the exemplary embodiments above, an arc ion plating apparatus is used as the deposition equipment forming the ESD protection device 10 of the disclosure, but the disclosure is not limited thereto, and in the case that the ESD protection device 10 having the ESD protection composite structure 140 of the disclosure may be formed using the same deposition equipment and the same metal source, other physical vapor deposition equipment or chemical vapor deposition equipment may also be used in the disclosure.

The ESD protection device 10 having the ESD protection composite structure 140 of the disclosure is described via FIG. 1D.

The ESD protection device 10 of the disclosure includes an ESD protection composite structure 140 and a substrate 100. The ESD protection composite structure 140 includes a link layer 110, a progressive layer 120, and a composite layer 130. The link layer 110 is disposed on the surface treatment layer 102 of the substrate 100, wherein the material of the link layer 110 includes a metal material. The progressive layer 120 is disposed on the link layer 110, wherein the material of the progressive layer 120 includes a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate 100 in a thickness direction of the progressive layer 120. The composite layer 130 is disposed on the progressive layer 120, wherein the material of the composite layer 130 includes a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material may make a sheet resistance value of the composite layer 130 1×10⁷ Ω/sq to 1×10⁸ Ω/sq. In an embodiment, metals in the metal material, the stoichiometric metal oxide material, and the non-stoichiometric metal oxide material in the ESD protection composite structure 140 are the same. Moreover, in an embodiment, the ESD protection composite structure 140 has a hardness of, for instance, 8 GPa to 12 GPa, a pencil hardness of, 5 to 7, an adhesion of, for instance, 8 N to 12N, a temperature resistance of, for instance, room temperature to 500° C., and a thickness of, for instance, 105 nm to 3000 nm.

In addition to the hardness, pencil hardness, adhesion, temperature resistance, and the thickness of the ESD protection composite structure 140, the material and specification of each member in the ESD protection device 10 are described in detail in the manufacturing method of FIG. 1A to FIG. 1D above and are therefore not repeated herein.

It may be known from the manufacturing method and the resulting ESD protection device that, by performing the surface treatment 200 on the substrate 100 and then forming the link layer 110 on the substrate 100 after the surface treatment, the adhesion of the link layer 110 and the substrate 100 (surface treatment layer 102) may be increased. Moreover, by forming the progressive layer 120 between the composite layer 130 and the link layer 110, the composite layer 130 having a stoichiometric metal oxide as the main component may be adhered well to the link layer 110 having a metal as the main component via the progressive layer 120. As a result, the ESD protection composite structure 140 of the disclosure has good adhesion with the substrate 100 as a whole. In the case that the adhesion between the ESD protection composite structure 140 and the substrate 100 is good, since the ESD protection composite structure 140 is not readily peeled off, the ESD protection device 100 of the disclosure may also have high hardness and high pencil hardness.

Moreover, based on the material (metal material, non-stoichiometric metal oxide material, and a mixture of stoichiometric metal oxide material and non-stoichiometric metal oxide material) of each layer of the ESD protection composite structure of the disclosure, the ESD protection composite structure of the disclosure as a whole may have high-temperature resistance properties. Moreover, since the material of the composite layer 130 of the topmost layer may obtain a sheet resistance value of 1×10⁷ Ω/sq to 1×10⁸ Ω/sq suitable for ESD protection application by mixing a non-stoichiometric metal oxide material of a specific ratio in the stoichiometric metal oxide material, good ESD protection properties may be obtained, and good acid and alkali corrosion resistance properties may be obtained based on the properties of the stoichiometric metal oxide material.

Moreover, it may be known from the manufacturing method above that, all of the films of FIG. 1A to FIG. 1D of the disclosure may be completed using the same deposition equipment (arc ion plating apparatus) and using the same metal source (metal target). In particular, the progressive layer 120 and the composite layer 130 having the properties of the disclosure may be formed by adjusting the flow of the reaction gas (oxygen plasma), and therefore the manufacturing method of the disclosure may be simplified. Moreover, since in the disclosure, a metal target is used as the common metal source of each layer in the ESD protection composite structure, the metal target is relatively cheap and having a large process area to facilitate industrialization. Based on the above, in the disclosure, an ESD protection device having an ESD protection composite structure having good ESD protection properties, high-temperature resistance, high mechanical properties, and high acid and alkali corrosion resistance properties may be manufactured via a cheap and simple manufacturing method.

Experimental Examples

<Manufacture of ESD Protection Device>

An arc ion plating apparatus was used to form a test piece of an ESD protection device having the ESD protection composite structure of the disclosure on a test substrate (experimental examples 1 to 4). The observation results of the resulting test pieces of experimental examples 1 to 4 show that the resulting films are complete and do not show signs of peeling. Moreover, the sheet resistance values obtained in a sheet resistance value test performed on the test pieces of experimental examples 1 to 4 are all in the range of 1×10⁷ Ω/sq to 1×10⁸ Ω/sq. The test results of experimental examples 1 to 4 are provided in Table 1.

TABLE 1 Experimental Experimental Experimental Experimental example 1 example 2 example 3 example 4 Substrate Al Al Al Al Target Ti Ti Ti Ti Surface Plasma Oxygen/argon Oxygen/argon Oxygen/argon Oxygen/argon treatment Process 650 700 750 850 bias (V) Link layer Process 0.850 0.750 0.750 0.850 current density (A/cm²) Process 300 300 300 300 bias (V) Progressive Process 0.850 0.750 0.750 0.850 layer current density (A/cm²) Process 250 250 250 250 bias (V) Oxygen 60 60 80 80 flow Composite Process 0.750 0.650 0.650 0.650 layer current density (A/cm²) Process 100 100 100 100 bias (V) Oxygen 90 90 120 150 flow Thickness (nm) of 1800 1800 1800 1800 ESD protection composite structure Film integrity No peeling No peeling No peeling No peeling Sheet resistance 1 × 10⁷ to 1 × 10⁷ to 1 × 10⁷ to 1 × 10⁷ to value (Ω/sq) 1 × 10⁸ 1 × 10⁸ 1 × 10⁸ 1 × 10⁸ Film integrity after No peeling No peeling No peeling No peeling temperature resistance test Sheet resistance 1 × 10⁷ to 1 × 10⁷ to 1 × 10⁷ to 1 × 10⁷ to value (Ω/sq) after 1 × 10⁸ 1 × 10⁸ 1 × 10⁸ 1 × 10⁸ temperature resistance test Pencil hardness ≥6H ≥6H ≥6H ≥6H

<Temperature Resistance Test and Electrical Property Test of ESD Protection Device>

FIG. 2 shows a heating curve of an RTA temperature test of the disclosure and a heating curve of an industrial reflow process. In FIG. 2, the heating curve of the industrial reflow process represented by a solid line is the standard for a high-temperature process generally used in current industries, and in the disclosure, a temperature resistance test was performed using a stricter (high temperature) standard than the industrial reflow process represented by the dotted line. Next, 50 RTA temperature tests were performed on the test pieces of experimental examples 1 to 4 using the heating curve shown by the dotted line of FIG. 2. After the tests, the surface of each test piece was inspected to confirm the surface of each test piece remained intact and the film did not peel off due to the high-temperature process. Next, a sheet resistance value test was performed on the test pieces after the RTA temperature tests, and the measured sheet resistances were all in the range of 1×10⁷ Ω/sq to 1×10⁸ Ω/sq. It may be known from the above tests that, the ESD protection device of the disclosure has good temperature resistance properties higher than current industrial standards and good adhesion for a substrate, and has good ESD protection properties. Moreover, the test results of experimental examples 1 to 4 are provided in Table 1.

<Acid and Alkali Corrosion Resistance Test of ESD Protection Device>

A 15 cm×15 cm 304 stainless steel was used as a substrate, and test pieces with thickness of 1500 nm and 2500 nm of an ESD protection composite structure were respectively manufactured. Next, a blank sheet (304 stainless steel substrate without an ESD protection composite structure), the 1500 nm test piece, and the 2500 nm test piece were respectively brought in contact with sulfuric acid (H₂SO₄) and potassium hydroxide (KOH), and then the current density of the blank piece and each test piece was measured. The measured results are shown in FIG. 3. It may be known from FIG. 3 that, the current density measured using the blank sheet (thickness: 0 nm) after the sulfuric acid treatment was 5.11×10⁻⁵ A/cm², and the current density was reduced to 1.15×10⁻⁷ A/cm² as the film thickness of the ESD protection composite structure of the test piece was increased. The current density measured using the blank sheet (thickness: 0 nm) after the sodium hydroxide treatment was 2.07×10⁻⁶ A/cm², and the current density was reduced to 2.24×10⁻⁷ A/cm² as the film thickness of the ESD protection composite structure of the test piece was increased. The reduction of current density here refers to good acid and alkali corrosion resistance, and therefore the ESD protection device of the disclosure has good acid and alkali corrosion resistance.

<Pencil Hardness Test of ESD Protection Device>

A pencil hardness test was performed on the test pieces of experimental examples 1 to 4 using a pencil hardness tester. The test results show that, the pencil hardnesses of the test pieces of experimental examples 1 to 4 are all 6 H or above, and therefore the ESD protection device of the disclosure has good hardness properties. Moreover, the test results of experimental examples 1 to 4 are provided in Table 1.

Based on the above, the ESD protection composite structure of the disclosure has a composite structure formed by a link layer (metal material)/progressive layer (non-stoichiometric metal oxide material having an oxygen concentration varying with film thickness)/composite layer (for which a stoichiometric metal oxide material used as the main component is mixed with a non-stoichiometric metal oxide material and having a sheet resistance value suitable for ESD protection application). In particular, the ESD protection composite structure has good adhesion with the substrate as a whole via the link layer and the progressive layer, ESD protection properties and acid and alkali corrosion resistance properties are provided via the composite layer, high-temperature resistance properties are provided via each layer material of the ESD protection composite structure, and the ESD protection composite structure further has high hardness and high pencil hardness via good adhesion. Therefore, the ESD protection device having the ESD protection composite structure of the disclosure may have all of good ESD protection properties, high-temperature resistance, high mechanical properties (adhesion, hardness, and pencil hardness), and high acid and alkali corrosion resistance properties.

Moreover, the ESD protection device of the disclosure may be completed using the same deposition equipment (arc ion plating apparatus) and using the same metal source (metal target). In particular, the progressive layer and composite layer having the properties of the disclosure may be formed by adjusting the flow of the reaction gas, and therefore the manufacturing method of the disclosure may be simplified. Moreover, since in the disclosure, a metal target is used as the common metal source of each layer in the ESD protection composite structure, the metal target is relatively cheap and having a large process area to facilitate industrialization. Therefore, in the disclosure, an ESD protection composite structure and an ESD protection device with all the good properties of the disclosure may be manufactured via a cheap and simple manufacturing method.

It will be apparent to those skilled in the art that various modifications and variations may be made to the structure of the disclosed embodiments without departing from the scope or spirit of the disclosure. In view of the foregoing, it is intended that the disclosure cover modifications and variations of this disclosure provided they fall within the scope of the following claims and their equivalents. 

What is claimed is:
 1. An ESD protection composite structure, comprising: a link layer used for disposing the ESD protection composite structure on a substrate, wherein a material of the link layer comprises a metal material; a progressive layer disposed on the link layer, wherein a material of the progressive layer comprises a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate in a thickness direction of the progressive layer; and a composite layer disposed on the progressive layer, wherein the composite layer comprises a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer may make a sheet resistance value of the composite layer 1×10⁷ Ω/sq to 1×10⁸ Ω/sq.
 2. The ESD protection composite structure of claim 1, wherein metals in the metal material, the stoichiometric metal oxide material, and the non-stoichiometric metal oxide material are the same.
 3. The ESD protection composite structure of claim 1, wherein a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer is 0.005:1 to 0.01:1.
 4. The ESD protection composite structure of claim 1, wherein the metal material comprises Ti, Al, Cu, Ni, Cr, Ta, or V, the non-stoichiometric metal oxide material comprises TiOx, AlOx, CuOx, NiOx, CrOx, TaOx, or VOx, and 0<x<a stoichiometry of a metal oxide, and the stoichiometric metal oxide material comprises TiO₂, Al₂O₃, CuO, NiO, Cr₂O₃, Ta₂O₅, or V₂O₅.
 5. The ESD protection composite structure of claim 1, wherein the metal material is Ti, the non-stoichiometric metal oxide material is TiOx, the stoichiometric metal oxide material is TiO₂, and x in TiOx in the progressive layer is 0<x<1.5 and x in TiOx in the composite layer is 1.5<x<2.
 6. The ESD protection composite structure of claim 1, wherein a thickness of the ESD protection composite structure is 105 nm to 3000 nm.
 7. The ESD protection composite structure of claim 1, wherein the ESD protection composite structure has a hardness of 8 GPa to 12 GPa, a pencil hardness of 5 to 7, an adhesion of 8 N to 12 N, and a temperature resistance of a room temperature to 500° C.
 8. An ESD protection device, comprising: a substrate; and the ESD protection composite structure of claim 1 disposed on the substrate via a link layer.
 9. The ESD protection device of claim 8, wherein a material of the substrate comprises a metal material, a ceramic material, a resin material, or a combination of the materials.
 10. The ESD protection device of claim 9, wherein the metal material comprises stainless steel or aluminum, the ceramic material comprises TiO₂, Al₂O₃, CuO, NiO, Cr₂O₃, Ta₂O₅, or V₂O₅, and the resin material comprises polycarbonate, epoxy resin, polyvinyl chloride, polypropylene, or polyethylene terephthalate.
 11. The ESD protection device of claim 8, wherein a surface of the substrate has a surface treatment layer, and the link layer is formed on the surface treatment layer.
 12. The ESD protection device of claim 8, wherein metals in the metal material, the stoichiometric metal oxide material, and the non-stoichiometric metal oxide material are the same.
 13. The ESD protection device of claim 8, wherein a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer is 0.005:1 to 0.01:1.
 14. The ESD protection device of claim 8, wherein the metal material comprises Ti, Al, Cu, Ni, Cr, Ta, or V, the non-stoichiometric metal oxide material comprises TiOx, AlOx, CuOx, NiOx, CrOx, TaOx, or VOx, and 0<x<a stoichiometry of a metal oxide, and the stoichiometric metal oxide material comprises TiO₂, Al₂O₃, CuO, NiO, Cr₂O₃, Ta₂O₅, or V₂O₅.
 15. The ESD protection device of claim 8, wherein a material of the substrate is aluminum or stainless steel, the metal material is Ti, the non-stoichiometric metal oxide material is TiOx, the stoichiometric metal oxide material is TiO₂, and x in TiOx in the progressive layer is 0<x<1.5 and x in TiOx in the composite layer is 1.5<x<2.
 16. The ESD protection device of claim 8, wherein a thickness of the ESD protection composite structure is 105 nm to 3000 nm.
 17. The ESD protection device of claim 8, wherein the ESD protection composite structure has a hardness of 8 GPa to 12 GPa, a pencil hardness of 5 to 7, an adhesion of 8 N to 12 N, and a temperature resistance of a room temperature to 500° C.
 18. A manufacturing method of an ESD protection device comprising the following steps: A. performing a surface treatment on a substrate; B. forming a link layer on the substrate after the surface treatment, wherein a material of the link layer comprises a metal material; C. forming a progressive layer on the link layer, wherein a material of the progressive layer comprises a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate in a thickness direction of the progressive layer; and D. forming a composite layer on the progressive layer, wherein the composite layer comprises a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer may make a sheet resistance value of the composite layer 1×10⁷ Ω/sq to 1×10⁸ Ω/sq.
 19. The manufacturing method of the ESD protection device of claim 18, wherein a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer is 0.005:1 to 0.01:1.
 20. The manufacturing method of the ESD protection device of claim 18, wherein: step A comprises performing the surface treatment on the substrate using a plasma; step B comprises providing a metal source and depositing a metal ion produced by the metal source on the substrate; step C comprises providing an oxygen as a reaction gas at the same time the metal ion is provided by the metal source to deposit the resulting non-stoichiometric metal oxide material on the link layer, wherein a supply of the oxygen is gradually increased with a process time; and step D comprises providing an oxygen as a reaction gas at the same time the metal ion is provided by the metal source to deposit the resulting stoichiometric metal oxide material and non-stoichiometric metal oxide material on the progressive layer, wherein a supply of the oxygen is configured such that the ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the resulting composite layer may make a sheet resistance of the composite layer 1×10⁷ Ω/sq to 1×10⁸ Ω/sq.
 21. The manufacturing method of the ESD protection device of claim 20, wherein step A to step D are performed using a same deposition equipment, and a same metal source is used in step B to step D.
 22. The manufacturing method of the ESD protection device of claim 20, wherein the plasma used in step A comprises an oxygen/argon plasma.
 23. The manufacturing method of the ESD protection device of claim 20, wherein the metal source comprises a metal target, and the metal target comprises a Ti target, an Al target, a Cu target, a Ni target, a Cr target, a Ta target, or a V target.
 24. The manufacturing method of the ESD protection device of claim 20, wherein step A to step D are performed using an arc ion plating apparatus, and the Ti target is used as the metal source in step B to step D. 